TWI277621B - Photocurable resin composition and resin composition for plastics comprising the same - Google Patents

Abstract

A photocurable resin composition comprises a cationic polymerizable compound (A), an acrylic resin (B) and a cationic photopolymerization initiator (C), in which the acrylic resin (B) has a cationic polymerizable functional group, and the content of the component (A) is 30 to 95 parts by mass and the content of the component (B) is 5 to 70 parts by mass, based on 100 parts by mass of the total amount of the components (A) and (B). In addition, the functional group of the acrylic resin (B) preferably contains at least one of a cyclic ether group, a vinyloxy group, an acid adduct of a vinyloxy group, and an active hydrogen group, with the active hydrogen group being a hydroxyl group is more preferable. The photocurable resin composition which has sufficient curability and sufficient adhesiveness to rigid plastics such as polycarbonate and PET having poor adhesive property.

Description

[Brief Description of the Invention] [Technical Field] The present invention relates to a photocurable resin composition which is used for a paint, an adhesive, an ink or the like which is hardened by irradiation with light. It is especially used for difficult-to-bond hard plastics such as polycarbonate, P E T, and A B S resins. [Prior Art] In recent years, plastic materials have been widely used in the field of electronic information materials. For example, polycarbonates that are hard plastics are often used in mobile phones or compact discs. Similarly, P E T resin is used for the optical film, and A B S resin is used for the outer casing of the home appliance information device. In the process of product preparation, there are steps for bonding, coating, and printing such hard plastics by light hardening, but these materials all have poor adhesion. Regarding the materials used for the coatings, adhesives, inks, and the like used in the above steps, it is necessary to impart a high degree of adhesion to the matrix resin.

As a method for imparting high adhesion, it is known to be effective in reducing the residual stress generated at the bonding interface by using a low degree of hardening shrinkage when the matrix resin is hardened. As a method for achieving such low-hardening shrinkage, there is a conventional epoxy resin or a ring which is hardened by a hardening system based on addition polymerization by photo-radical polymerization using an acrylic monomer or the like. A cation-opening photopolymerization hardening system of a ring-shaped scale such as oxypropylene (ο X etane) resin. However, this hardening system using cationic ring-opening photopolymerization is difficult to introduce the functional group which interacts with the hard plastic which is a bonded body, and the adhesion cannot be sufficiently provided. Thus, the cation is composed of an epoxy compound, a propylene oxide compound, a cationic light 6 326 \ patent specification (supplement) \94-11\94124674 1277621 polymerization initiator, a pigment as a colorant, and a pigment dispersant. In the ring photopolymerization system, a comb-type polymer having a fixing portion as a base and a liquid at room temperature is added as an active ingredient, and as a pigment dispersing agent, an adhesion property to the adherend is attempted, and it is found to be sufficient. Adhesion (for example, refer to Patent Document 1). However, since this system contains a basic substance, it can be a retarder (reaction inhibitor) in the polymerization of cationic ring-opening photopolymerization, so that it is impossible to exhibit a sufficient hardening speed required for productivity. [Patent Document 1] Japanese Patent Laid-Open No. 2 0 0 3 - 2 1 2 9 6 5

SUMMARY OF THE INVENTION (Problems to be Solved by the Invention) An object of the present invention is to provide a light having sufficient photocurability and having sufficient adhesion to a hard plastic which is difficult to bond and a hard plastic represented by PET. A curable resin composition. (Means for Solving the Problem) As a result of intensive research, the inventors of the present invention found that a cationic photopolymerization system composed of a cationically polymerizable compound such as an epoxy compound or a propylene oxide compound and a cationic photopolymerization initiator is added during hardening. As a result of the specific acrylic resin to which the cationically polymerizable functional group was added, it was found that sufficient curability and adhesion were exhibited, and thus the present invention was completed. That is, the present invention is a photocurable resin composition characterized by having (A) a cationically polymerizable compound, (B) an acrylic resin, and (C) a cationic photopolymerization initiator, wherein the (B) acrylic resin has a cation The polymerizable functional group is, in a total of 100 parts by mass of (A) and (B), (A) is from 3 to 9 parts by mass, and (B) is from 5 to 70 parts by mass. 326\Patent Specification (Supplement)\94-11 \94124674 1277621 Further, the cyclic ether and the active base. Ethene conversion as a base, and further into Φ made of rubber oil (invention? This issue is also closely related to the test after the tree plastic

[Implementation of the following [(A) cations having a cyclic ether-like ester; as a functional group of the (B) acrylonitrile-based resin, preferably a group containing a vinyloxy group, B The dilute oxy acid addition product is any one or more of hydrogen groups, and further preferably, the active hydrogen group is further, and (B) the weight average molecular weight of the acrylic resin (poly phenyl) is 1 0 0 0 Preferably, it is in the range of ~1 0 0,0 0 0. (A) The cationically polymerizable compound preferably contains a cyclic ether. One step preferably contains an epoxy group and/or a propylene group. The present invention is a coating composition for a plastic containing the photocurable resin composition described above, a binder composition for a plastic, and a composition for a plastic ink. [Fruit] The light-curable resin composition of the bright one has sufficient hardenability, and a hard plastic which is difficult to bond, such as polycarbonate or P E T, can maintain the same adhesion at an accelerated speed. Further, when the optically hard resin composition of the present invention is used, a coating material, an adhesive, an ink, various sealing materials, and the like which are used for a hard member such as polycarbonate or PET can be used. Modes The present invention will be described in detail. Ionic polymerizable compound] The (A) cationically polymerizable compound used in the present invention is one cationically polymerizable functional group in one molecular chain. Specifically, it refers to a compound such as a molecular oxirane (ο X irane ring), a propylene propylene ring, a tetrahydrofuran or the like; a cyclic diterpene acetal; a cyclic carbonate; a cycloethene; The cyclic thioether (c-pyran); a cyclic olefin; a styrene 8 326 \ patent specification (supplement) \94-11 \94124674 1277621 is not particularly limited as long as it has cationic polymerizability. Among these, a compound having an epoxy group or a compound having an oxypropylene group is preferred. In this case, an epoxy group and an oxypropylene group may be contained at the same time. <epoxy compound>

Specific examples of the epoxy group-containing compound are as follows: a specific example of a compound containing one epoxy group is phenyl glycidol &|, butyl glycidol, etc.; and a compound containing two or more epoxy groups may be used. Illustrative examples of hexanediol diglycidyl ether, tetraethylene glycol diglycidyl ether, tris(hydroxymethyl)propane triglycidyl, bis-A diglycidyl ether, bis-F diglycidyl ether, and western acid resin (η 〇v ο 1 ak ) glycidyl ether, hexahydro S too glycidol, dimer acid glycidyl ester, tetraglycidylamino diphenyl decane, 3,4-epoxy-6-fluorenyl Cyclohexyl decyl decanoate, triglycidyl isocyanate, 3,4-epoxycyclohexyl decyl carboxylate, polypropylene diglycidyl ether, polybutadiene or polysulfide A glycidyl ether or the like such as a modified product. Further, an alicyclic ring such as 3,4-epoxycyclohexyldecyl-3,4-epoxycyclohexanecarboxylate or bis(3,4-epoxycyclohexyl) adipate may also be mentioned. Epoxy compound. Further, among the cyclic ethers of the three-membered ring which is the same as the epoxy group, a compound having a functional group represented by [Chemical Formula 1] is also supplied to the component (A) of the present invention:

(In [Chemical Formula 1], R! and R 2 are carbon atoms, and the carbon atom is saturated or not 9 326\patent specification (supplement)\94-11 \94124674

1277621 Saturated. R 3 is a hydrogen atom or a carbon atom, and the carbon atom is saturated or has at least one ring group represented by [Chemical Formula 1] in one molecular chain, and has at least one compound in one molecular chain. An oxirane ring-based compound characterized in that, in a carbon atom forming an epoxy, one carbon atom is substituted with at least one hydrogen atom and the carbon atom is substituted with two carbon atoms, and the sum of the substituted carbon atoms Bonding or unsaturated bonding. Further, the saturated bond and the bond of the carbon atom may be substituted with any atomic group. Specifically, 1 and R2 represent a hydrocarbon composed of a paraffin, an olefin, or any of them, and may have a substituent. The alkyl group, the naphthenic hydrocarbon, the aromatic ring, the iS element, the hydroxyl group, the ketone, the ester group, the alkyl group substituted with an alkyl group, and the alkyl group are substituted, but are not particularly limited. Further, R3 represents a hydrogen atom or a hydrocarbon composed of any one of an olefinic hydrocarbon and an acetylene hydrocarbon, which is also a substituent. The substituent may, for example, be an alkyl group, a cycloalkane ring, a halogen, a thiol group, an acid, a ketone or a ketone group, but is not limited. More specifically, examples of the compound having an oxirane ring group represented by at least 1 1 in a molecular chain include terpinolene dioxide, oxygen, and oxygen. Deuterated bismuth, 2-mercapto-dehydroglycerin, cerium oxide, methyl 2-mercaptoate, oxiranyl 7-oxa-bicyclo[4.1.0]heptane, 2 曱Ethylene oxide, 2-(benzyloxyindenyl)-2-methylepoxyepoxy-4,7-nonanol (methano)-l-oxaspiro-(2,5-)-octyl Too 326\patent specification (supplement)\94-11 \94124674 10 Not saturated. An ethane ring group represented by oxyethylene ring 1], the other one is a saturated or unsaturated acetylene hydrocarbon > substituent, an ether, an acid, an amine group, etc., a paraffin hydrocarbon, which may have Aromatically, the aromatics are particularly affected by [di-cappedadiene, oxygen dehydroglycerol-acetonitrile-2, pyroline, 5,6-ethyl, 2-mercapto

1277621 -1 -1 -2 -methyl-epoxyethylidene)-indolyl-3-a-indolyl alcohol, dioxide, etc., especially as a dioxide dioxide on the cover of two women, cerium oxide, ethylene oxide - Bicyclo [4 · 1 . 0 ] heptane, 5,6-epoxy-4,7-nonanol-;!-oxaspiro-octane or lauric oleate, with a minimum of 14 1 in the molecule] The specific oxirane ring structure shown is sufficient, so that it has a cationically polymerizable oxime/epoxy propylene compound such as another oxirane ring in the same color. Specific examples of the compound having an oxypropyl group include 3-ethyl-3-oxopropane, 3-ethyl-3-phenoxymercaptopropene oxide, and 3-ethylethyl. Hexyloxyindenyl) propylene oxide, 3-ethyl-3-(triethoxydecyloxydecyl) propylene oxide, 3-cyclohexyloxyindol-3-ethylepoxy 1^ A specific example of a compound having two propylene oxide rings, which is (3-ethyl-3-epoxypropenyl fluorenyl) ether, 1,4 - bis{[(3-ethyl-propenyl) decyloxy ] 曱 base} benzene and so on. Specific examples of the compound having three or more cyclic rings include tris(hydroxymethyl)propane ginseng (-3-glycidyl fluorenyl) ether and isovalerol ginseng (3-ethyl-) 3-cyclic fluorenyl)ether, isovalerol bismuth (3-ethyl-3-epoxypropenyl hydrazide) diisopentyltetraol (3-ethyl-3-epoxypropanyl fluorenyl) ether These cationically polymerizable compounds may be used singly or in combination of two, but it is preferred to use an epoxy group-containing compound together with a compound containing a burnt group. [(B) Acrylic resin] 326\Patent Instruction manual (supplement)\94-11\94124674 11 Cinnamon oil baking base 7-oxygen (2,5)-3 [Chemical one molecular skeleton also 1 ring methyl ring-3-(2-alkylpropane 3 burning) Etc. bis 3-epoxyoxypropanol 3-ethyloxypropanone k) ether, above-mentioned epoxy propylene 1277621 (B) acrylic resin used in the present invention is characterized by containing a cationically polymerizable functional group That is, when curing by cationic ring-opening photopolymerization, the component (B) acrylic resin may be any of the basic reactions such as initiation, growth, shutdown, chain transfer, etc. during cationic polymerization. The basic reaction involved in the key of (A) a cationic polymerizable compound into crosslinked covalently by its characteristics.

With respect to each of the basic reactions, a cyclic ether group can be used as a functional group capable of causing a terminal at the initiation reaction of the cation ring-opening polymerization. The cyclic ether group is added by a proton generated by a cationic photopolymerization initiator to produce an oxonium ion which can be a terminal. Further, the initiating terminal of the cationic addition polymerization also has a ring-opening polymerization for a cyclic ether, an ethyleneoxy group which is a functional group capable of generating carbocation, and an ethylene group formed from an acid port. The construction is also useful in the present invention. In the functional group to be introduced by chain transfer or termination, an active hydrogen group is exemplified, and examples of the active hydrogen group include a hydroxyl group, a thiol group, and an amine group. Among them, a trans group is most suitable. Next, the functional group introduced by the growth reaction of the cationic ring-opening polymerization may, for example, be a cyclic ether group as exemplified above. The functional group of each basic reaction is exemplified below, and any of the above-mentioned initiation, growth, cessation, chain transfer, and the like may be carried out, and is not limited to the functional groups shown below. It is preferable to contain an industrially significant functional group which is a raw material sold in the market as a raw material, and it is preferable to contain an acid adduct selected from a cyclic ether group, a vinyloxy group, a vinyloxy group, and an active hydrogen group. More than one. In the case of an active hydrogen group, a carboxylic acid, a hydroxyl group, a thiol group or an amine group is preferred, and a hydroxyl group is further preferred. The hydroxyl group is an alcoholic hydroxyl group or a phenolic hydroxyl group, and is preferably an alcoholic hydroxyl group. Hereinafter, the method of introducing these functional groups will be described.

In general, as a method of introducing a functional group into an acrylic resin, a radical polymerizable monomer having a functional group is subjected to radical copolymerization with another radical polymerizable monomer to introduce a functional group into a polymer side chain. a method, or a radical polymerization initiator having a functional group or a functional group having a diethanol sulfide or the like in an initiator such as 2, 2'-azobis(2-hydroxydecylpropionitrile) during radical polymerization A chain transfer agent whereby a functional group is introduced into the end of the polymer molecule. The above-mentioned radically polymerizable monomer having a functional group as exemplified above is specifically exemplified. Examples of the radically polymerizable monomer having a cyclic ether group in a side chain include a (fluorenyl) acrylate monomer having a cyclic ether group in a side chain, and more specifically, a glycidyl group is mentioned. Glycidyl (mercapto) acrylate, 3-ethyl-3-epoxypropaneethyl (meth) acrylate having propylene oxide group, 3,4-epoxy ring having alicyclic epoxy group Hexylmethyl(fluorenyl)acrylic acid, anthracenyl glycidyl methacrylate having a substituted methyl group at a glycidyl group, tetrahydrofuranyl (meth)acrylic acid having a tetrahydrofuran ring, and the like. Examples of the radically polymerizable monomer having a vinyloxy group in a side chain include 2-(ethoxyethoxyethoxy)ethyl group having a propylene baking base and an ethyleneoxy group in one molecule. )Acrylate. Further, a structure in which an acid such as acetic acid, trifluoroacetic acid or hydrochloric acid is further added to the ethyleneoxy group is also used in the present invention. As the radical polymerizable monomer having a hydroxyl group in a side chain, as long as, for example, 2-hydroxyethyl (mercapto) acrylate, hydroxypropyl (decyl) acrylate, 2-hydroxyethyl (fluorenyl) 13 326 Patent specification (supplement)\94-11\94124674

1277621 Acrylate ε-caprolactone ring-opening adduct, (mercapto) propylene oxyethane and/or propylene oxide mixed and/or separate adducts having a hydroxyl group, which is not particularly limited . Further, a functional group which potentially generates a hydroxyl group due to the action such as (2-methyl-1,3-diepoxide:): half (dioxolane-4-yl)methyl (indenyl) An acetal structure, a benzyl group, a tert-butyl group, and also used in the present (B) acrylic acid resin system generally means a radical polymerizable monomer having a functional group as in the side chain and other radical polymerization Φ copolymerization. Things. The other radical polymerizable monomer may, for example, be an enoate. As the ester group of the (fluorenyl) acrylate, it has a mercapto group, an ethyl group, an isopropyl group, a n-butyl group, an isobutyl group, a 2-ethylhexyl group, a cyclohexyl group, a benzyl group, an isodecyl group, A non-functional alkyl ester of a lauryl group or the like, which may be a linear or branched structure, may be copolymerized with a (fluorenyl) acrylate such as styrene, α-ene, vinyl acetate or the like, and may be used as a constituent. According to the invention, the above-mentioned radical polymerization having a functional group in a side chain and other radical polymerizable monomers can be organically used by using an organic peroxynitride compound as a radical polymerization initiator. The solvent is subjected to radical polymerization to obtain a copolymer, and the resin liquid containing the solvent containing the copolymer may be directly removed by a solvent removal agent, whereby an acrylic resin may be obtained and used as an acrylic resin. The content of the functional group is preferably from 1 to 50% by weight, and preferably from 1 to 30% by weight, from the viewpoint of curability. Further, the ring of the present invention/acid ester is in the form of a 2-chain ethyl acrylate such as a side chain acid catalyst. The exemplified (mercapto) propylene is preferably a tributyl group or a myristyl group. Furthermore, mercaptophene. The comonomer or the singly is passed through, but it will be dissolved as (B). The base is used for the special t (B) (B) 326\patent specification (supplement)\94-11\94124674 14 1277621 The average weight molecular weight (in terms of polystyrene) of the acrylic resin measured by GPC, From the viewpoint of durability or adhesion, it is usually 1,0 0 0 to 1 0 0, 0 0 0, and preferably 1,0 0 0 to 5 0,0 0 0. [(C) Cationic photopolymerization initiator] The (C) cationic photopolymerization initiator used in the present invention is a compound which generates a cation or a Lewis acid by light.

Examples of the phosphonium salt compound which generates a cationic species or a Lewis acid by an active energy ray include diphenyl iodine rust, 4-methoxy diphenyl iodine rust, bis(4-nonylphenyl) iodine rust, and double (4-T-butylphenyl) iodonium, bis(dodecylphenyl) iodine, triphenylsulfonium, diphenyl-4-thiophenoxyphenylhydrazine, bis[4-(two Phenylfluorenyl)-phenyl]sulfide, bis[4-(bis(4-(2-hydroxyethyl)phenyl)indolyl)-phenyl]sulfide, 5-2,4-cyclopentadiene Base) [1,2,3,4,5,6 - 7? -(decylethyl)benzene]-iron (Γ) and other rust ions with tetrafluoroborate, hexafluorophosphate, hexafluoroantimonate A compound composed of a combination of anions such as hexafluoroarsenate or hexachloroantimonate. Further, as a commercially available rust salt of a cationic species or a Lewis acid by an active energy ray, Uvacure 1590 and 1591 (the above are manufactured by DAICELUCB Co., Ltd., trade name); San-Aid SI-110, SI-180, SI-100L > SI -80L, SI-60L (above is Sanshin Chemical Industry Co., Ltd., trade name); ADEKA Optomer SP-100, SP - 1 7 2, SP - 1 70, SP - 1 5 2 ( The above is manufactured by Asahi Kasei Co., Ltd., trade name); 2 0 7 4 (Rh 〇dia company, product name). The above cationic photopolymerization initiators may be used singly or in combination of two or more. It can also be added with sensitizers such as 9-oxosulfide or 2-ethylhydrazine-8. Further, the active energy ray and heat may be used in combination to carry out polymerization. 15 326\Patent specification (supplement)\94-11 \94124674 1277621 The above components (A), (B), and (C) will exhibit better hardenability and adhesion at a specific blending ratio. That is, in the total of 100 parts by mass of (A) and (B), (A) is 3 0 to 9 5 (parts by mass), and (B) is 5 to 70 (parts by mass), preferably (A) is 5 0 to 9 5 (parts by mass), and (B) is 5 to 5 0 (parts by mass). If the blending amount of (A) and (B) is within this range, it is preferable from the viewpoint of hardenability and adhesion. The blending amount of (C) is from 0 to 5 parts by mass based on the total of 100 parts by mass of (A) and (B). When the amount of the compound (C) is within this range, it is preferable from the viewpoints of hardenability, water resistance, coloring of the resin, and the like.

In the composition of the present invention, other resins may be used as needed. Examples of other resin components include polybutadiene, polybutadiene, polyether, polyester, styrene-butadiene-styrene block copolymer, petroleum resin, diterpene benzene resin, and ketone. A resin, a cellulose resin, a fluorine-based oligomer, a polyoxymethylene oligomer, a polysulfide-based oligomer, or the like. These resins may be used singly or in combination of two or more. Examples of the modifier include a polymerization initiation aid (photosensitizer), an aging inhibitor, a leveling agent, a wettability improver, an adhesion-imparting agent, a surfactant, a plasticizer, and a light absorber. These modifiers may be used alone or in combination of two or more. A diluent may be used for the imparting or enhancing of coating properties. As the diluent, a common organic solvent or a previously described monofunctional cyclic ether can be used. The present invention has sufficient photocurability and is a photocurable resin composition having sufficient adhesion to a hard plastic which is difficult to bond, and a hard plastic represented by PET. Therefore, coating of such a plastic can be used. Use the composition. Further, it can be used for an adhesive, an adhesive for ink, and the like. Furthermore, it is possible to use the 326\Patent Specification (supplement)\94-11 \94124674 16 © 1277621, which has recently required a high protective coating agent or [Examples], based on the evaluation of the hardenability and the comparative example (hardening property) ) Photohardenable ® carbonate plate and polygly-coated, metal-halide polycarbonate plate surface will be hardened and not tacky (adhesive). Light-curing type carbonic acid vinegar plate or poly

On, use metal halide JIS K5400 8. Test. In addition, in the case of the manufacturing method, the material for the optical disk of the adhesiveness and the workability of the optical disk, especially the adhesive for the optical disk, after the reflowing of the cooling machine and the 355 manufacturing apparatus under nitrogen gas. The invention will be specifically described by way of examples and comparative examples. Further, the adhesion is carried out in accordance with the following methods and the ratios. The resin composition was applied to a polyethylene terephthalate (PET) plate (4.5 cmx2. OcmxO. 2 cm) using a coater at 100 ° m for 1 J / c m2 irradiation. The degree of hardening of the topcoat film immediately after the irradiation was visually evaluated. Degree of hardening The tackiness (t a c k ) is shown in 〇, only the surface hardened or the surface is shown as △, and the completely unhardened one is shown as X. The resin composition was applied to a polyethylene terephthalate (PET) plate (4·5 cm x 2. Ocm x 0.2 cm) using a coater at 100 ° m for 1 J / c m 2 irradiation. This coating film was adhered according to 5.2, using 2 m square, 25 squares. The test piece was stored in a thermostat humidifier at 85 ° C X 80% to carry out an adhesion test. Diphenylbenzene 34.0 g was placed in an acrylic resin composition having a content of 2 L in a blender, a thermometer, a tank, or the like, and the temperature was raised to a polymerization temperature of 1 3 5 °C. For the time of 4 hours 17 326 \ patent specification (supplement) \94-11 \94124674 1277621, the amount of decyl acrylate as a radical polymerizable monomer 400g, phenyl bake 50g, 2 - A mixture of 50 g of ethylmercaptopropionate and 20 g of 2-butylhexanoate as a radical initiator was mixed. After the end of the dropwise addition, stirring was continued at a temperature of 1 3 5 ° C for 1 hour. Then, the manufacturing apparatus was vacuumed to distill off quinone and residual monomers to obtain (B) a propionate-based resin. [Manufacturing Examples 2 to 6, 8]

The same procedure as in Production Example 1 was carried out except that the amounts of the radical polymerizable monomer and the radical initiator shown in Table 1 were changed. [Production Example 7] The same procedure as in Production Example 1 was carried out except that the radical polymerizable monomer and the radical initiator amount shown in Table 1 were changed and the polymerization temperature was changed to 100 °C. [Example 1] 10 parts by mass of the acrylic resin obtained in Production Example 1 of (B), and a hydrogenated bisphenol A type epoxy resin (Akasu resin EP-4080S, manufactured by Asahi Kasei Co., Ltd.) 30 parts by mass of bis [1-ethyl(3-ethoxypropenyl)] fluorenyl (Aron oxetane OXT-221, manufactured by Toagosei Co., Ltd.), placed in a light-shielding brown bottle, and heated and stirred to confirm (A) Forms a completely uniform shape with (B). Then, when the temperature of the mixed resin liquid reaches 60 ° C or lower, (toluylcumyl phenyl) iodonium (pentafluorophenyl) borate is mixed and dissolved as (C) cationic polymerization initiator ( RhoDORSIL PH0T0INITIAT0R 2074), 3 parts by mass, to obtain a photocurable resin composition. The cationically polymerizable resin composition was evaluated in accordance with the aforementioned evaluation method. The results are not shown in Table 3 in the results of the evaluation of 18 326\patent specification (supplement)\94-11 \94124674 1277621. [Examples 2 to 1 1] In the same manner as in Example 1, except that the types and amounts of the component (A), the component (b), and the component (C) shown in Table 2 were changed, the evaluation was carried out, and the results were shown. In Table 3. Further, regarding Example 4, the adhesion to the polyethylene terephthalate plate was tested, and the results are shown in Table 4. [Comparative Example 1] ® 70 parts by mass of hydrogenated bisphenol a type epoxy resin (ADEKAresin EP - 4080S, manufactured by Asahi Kasei Co., Ltd.) and two U-ethyl (3-¥) in a light-shielding brown bottle Oxypropyl propyl)] fluorenyl _ (Aron ο X etane 0 XT - 2 2 1 manufactured by Toagosei Co., Ltd.) 30 parts by mass of (nonylphenyl cumyl) iodine as (c) cationic polymerization initiator Ruthenium (pentafluorophenyl)boron g-sodium salt (RHODORSIL PHOTOINITIATOR 2074, manufactured by Rh〇dia Co., Ltd.) 3 parts by mass dissolved and dissolved to obtain a photocurable resin composition. The photocurable resin composition was evaluated in accordance with the above evaluation method, and the results are shown in Table 3. Further, the adhesion test to the polyethylene terephthalate plate was carried out, and the results are shown in Table 4. [Comparative Example 2] In a light-shielding brown bottle, 68 parts by mass of hydrogenated bisphenol A type epoxy resin (ADEKA resin EP - 4080S, manufactured by Asahi Kasei Co., Ltd.) and bis [1-ethyl (3) were used. -Epoxypropenyl)]decyl ether (Aron oxetane 0XT-2 2 1 manufactured by Toagosei Co., Ltd.) 30 parts by mass of (nonylphenyl cumyl) iodonium as (c) cationic polymerization initiator (Pentafluorophenyl)borate (Rhodia 19 326\patent specification (supplement)\94-11\94124674 1277621 company, RHODORSIL PHOTOINITIATOR 2074) 3 parts by mass dissolved. This is a blend of 2 parts by mass of a comb-type polymer which is a base and has a liquid at room temperature as disclosed in Japanese Patent Laid-Open Publication No. Hei 2 0 0 3 - 2 1 2 9 5 5 Ethylimine)-poly(1,2-hydroxystearic acid) graft polymer (Solsperse 28000, manufactured by Avecia Co., Ltd.) to obtain a photocurable resin composition. The results of evaluation of the photocurable resin composition in accordance with the above evaluation method are shown in Table 3. [Comparative Example 3] 1 part by mass of the acrylic resin obtained in Production Example 6 of (B), and a hydrogenated bisphenol A type epoxy resin (AKA resin EP-4080S, manufactured by Asahi Kasei Co., Ltd.) 60 parts by mass and bis [1-ethyl(3-ethoxypropenyl)] fluorenyl (Aron oxetane 0X butyl-221) 30 parts by weight, placed in a light-shielding brown bottle, heated and stirred, and confirmed (A) and (B) form a completely uniform shape. Then, when the temperature of the mixed resin liquid reaches 6 〇I or less, 'mixing and dissolving (toluyl cumyl) iodonium (pentafluorophenyl) borate as the (C) cationic polymerization initiator (Rhodia) The company made, RHODORSIL PH0T0INITIAT0R 2074) 3 parts by mass to obtain a photocurable resin composition. The results of evaluation of the photocurable resin composition in accordance with the above evaluation method are shown in Table 3. 326\Patent Specification (Repair)\94-11 \94124674 1277621 Table 1 '^—----__ Manufacturing Example 1 Manufacturing Example 2 Manufacturing Example 3 Manufacturing Example 4 Manufacturing Example 5 Manufacturing Example 6 Manufacturing Example 7 Manufacturing Example 8 Functional group free 2-hydroxyethyl methacrylate acrylic 10 5 10 10 radical polymerization r-monomeric glycidyl fluorenyl acrylate 10 5 3-ethyl-3-epoxypropylethyl sulfonyl Acrylic vinegar 10 2-(vinyloxyethoxy)ethyl methacrylate 10 Non-functional free radical thiol acrylate 80 80 80 80 80 85 80 80 Polymeric styrene styrene 10 10 10 10 10 15 10 10 Free radical initiator tert-butyl 2-ethylhexanoate 4 4 4 4 4 4 0.05 15 Weight average molecular weight (polystyrene conversion) 12000 13000 11000 25000 13000 12000 200000 900 Table 2 Example Mm Example 1 Example 2 Example 3 Cargo Example 4 Example 5 Example 6 Example? Example 8 Example 9 Example 10 Example 11 tbfe Example 1 Example 2 t off 3 ADEKA resin EP-4080S 60 60 60 60 60 30 30 60 60 15 65 70 68 60 EPOMIX R140 10 Composition EPICOAT 1007 10 (A) Aron oxetane OXT-221 30 30 30 30 30 30 25 30 30 15 30 30 30 30 ADEKA resin KRM2110 10 oxyethylene oxide 5 Production example 1 10 40 10 Production example 2 10 70 5 Production example 3 10 Component manufacturing example 4 10 (B Production Example 5 10 Production Example 6 Production Example 7 10 Production Example 8 10 Additive Solsperse 28000 2 Component (C) RHODORSIL PHOTOINITIATOR R2074 3 3 3 3 3 3 3 3 3 3 3 3 3 3 Table 3 Evaluation Item Example Comparative Example Example 1 Example 2 Example 3 Example 4 Example 5 Lion example 6 Example 7 Example 8 Example 9 Example 10 Example 11 tbfe Example 1 _H2 _ material 3 Harden 〇〇〇〇〇〇〇〇 〇Δ 〇〇X 〇 close! ·Infancy 25/25 25/25 25/25 25/25 25/25 25/25 25 /25 20/25 25/25 25/25 25/25 0/25 - 25/25 25/25 25/25 25/25 25/25 25/25 25/25 25/25 20/25 20/ after accelerated test 25 25/25 20/25 0/25 - 0/25 21 326\Patent Specification (Supplement)\94·11\94〗 24674 1277621 Table 4 Evaluation Item Example 4 Comparative Example 1 Early stage of hardenability 25/25 20/25 25/25 15/25 after accelerated test

326\ patent specification (supplement)\94-11 \94124674 22

Claims (1)

1277621 X. Patent application scope: 1. A photocurable resin composition comprising: (A) a cationically polymerizable compound, (B) an acrylic resin, and (C) a cationic photopolymerization initiator, (B) The acrylic resin has a cationically polymerizable functional group, and in a total of 100 parts by mass of (A) and (B), (A) is from 3 to 95 parts by mass, and (B) is from 5 to 70 parts by mass. 2. The photocurable resin composition of claim 1, wherein the cationically polymerizable functional group of the (B) acrylic resin contains a cyclic ether β group and an ethylene oxide (viny 1 ο X y ) group. Any one or more of an acid addition product of an ethylene bakeoxy group and an active hydrogen group. 3. The photocurable resin composition of claim 2, wherein (B) the active hydrogen group of the cationically polymerizable functional group of the acrylic resin is a hydroxyl group. F4. The photocurable resin composition of the first aspect of the patent application, wherein (B) the acrylic resin has a weight average molecular weight (in terms of polystyrene) in the range of 1,000 to 100,000. 5. The photocurable resin composition of claim 1, wherein the (A) cationically polymerizable compound contains a cyclic ether group. 6. The photocurable resin composition of claim 5, wherein the (A) cationically polymerizable compound contains an epoxy group and/or an oxetanyl group. A coating composition for plastics, which comprises the photocurable resin composition according to any one of claims 1 to 6. 8. A plastic adhesive composition characterized by comprising photohardening according to any one of items 1 to 6 of the application specification 23 326\patent specification (supplement)\94-11\94124674 1277621. A resin composition. A plastic ink composition comprising the photocurable resin composition according to any one of claims 1 to 6. 24 326\Patent specification (supplement)\94-11\94124674